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Acta Cryst. (2008). E64, m389-m390    [ doi:10.1107/S1600536807065671 ]

Tetraaquabis(2-oxo-1,2-dihydroquinoline-4-carboxylato-[kappa]O4)nickel(II)

G. Yuan, J.-S. Qin, Z.-M. Su, K.-Z. Shao and Y.-M. Fu

Abstract top

In the title compound, [Ni(C10H6NO3)2(H2O)4], the central NiII atom is located on an inversion center and coordinated in a slightly distorted octahedral geometry by two O atoms from two 2-oxo-1,2-dihydroquinoline-4-carboxylate ligands and four water molecules, all of which act as monodentate ligands. The crystal structure features an extensive network of intermolecular hydrogen-bonding interactions (O-H...O and N-H...O) and offset face-to-face [pi]-[pi] stacking interactions [centroid-centroid distances = 3.525 (3) and 3.281 (5) Å].

Comment top

Recently, the complexes based on quinoline-4-carboxylic acid have been reported (Bu et al., 2005; Xiong et al., 2000). However, the compounds built from 2-oxo-1,2-dihydroquinoline-4-carboxylic acid (dhqc) and transition metals have not been reported. When 2-hydroquinoline-4-carboxylic acid (hqc) and NiCl2 were employed as starting materials, the title compound, as shown in Fig. 1, was obtained. X-ray diffraction analysis has revealed that hqc exists mainly in the form of its tautomer dhqc, because the proton transfers from hydroxyl O atom to N atom under alkaline condition. Similar to the most mononuclear Ni complexes reported previously (Bai et al., 2007; Liu, 2007; Pang et al., 2007; Wu et al., 2007; Zhang et al., 2007), the NiII atom in the title compound, lying on an inversion center, is six-coordinated by four water molecules and two O atoms from two dhqc ligands (Table 1), forming a slightly distorted octahedral geometry. The molecules are linked into a three-dimensional network by a combination of intermolecular hydrogen bonds (O–H···O and N–H···O) (Table 2) and offset face-to-face π–π stacking interactions [centroid-to-centroid distances 3.525 (3) and 3.281 (5) Å].

Related literature top

For related literature, see: Bai et al. (2007); Bu et al. (2005); Liu (2007); Pang et al. (2007); Wu et al. (2007); Xiong et al. (2000); Zhang et al. (2007).

Experimental top

A mixture of 2-hydroxyquinoline-4-carboxylic acid (0.945 g, 5 mmol), NaOH(0.4 g, 10 mmol) and NiCl2.6H2O (2.3 g,10 mmol) in water (50 ml) was boiled for 20 min with stirring. Then the mixture was cooled to room temperature. The resulting solution was filtered and allowed to stand. After a week, green crystals of the title compound were obtained.

Refinement top

H atoms on C atoms and N atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å, N—H = 0.86Å and Uiso(H)=1.2Ueq(C,N). Water H atoms were located in a difference Fourier map and refined with a restraint of O—H = 0.85 (1) Å, and Uiso(H)=1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Siemens, 1990); software used to prepare material for publication: SHELXTL-Plus (Siemens, 1990).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1 - x, 2 - y, 1 - z.]
Tetraaquabis(2-oxo-1,2-dihydroquinoline-4-carboxylato-κO4)nickel(II) top
Crystal data top
[Ni(C10H6NO3)2(H2O)4]Z = 1
Mr = 507.07F000 = 262
Triclinic, P1Dx = 1.696 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71069 Å
a = 7.105 (5) ÅCell parameters from 2250 reflections
b = 8.507 (5) Åθ = 1.3–26.0º
c = 9.216 (5) ŵ = 1.04 mm−1
α = 108.723 (5)ºT = 293 (2) K
β = 108.396 (5)ºBlock, green
γ = 90.840 (5)º0.5 × 0.4 × 0.3 mm
V = 496.4 (5) Å3
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2250 independent reflections
Radiation source: fine-focus sealed tube2064 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 293(2) Kθmax = 28.3º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.601, Tmax = 0.721k = −8→11
3041 measured reflectionsl = −12→7
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.121  w = 1/[σ2(Fo2) + (0.0726P)2 + 0.4272P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2250 reflectionsΔρmax = 0.40 e Å−3
151 parametersΔρmin = −0.57 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C10H6NO3)2(H2O)4]γ = 90.840 (5)º
Mr = 507.07V = 496.4 (5) Å3
Triclinic, P1Z = 1
a = 7.105 (5) ÅMo Kα
b = 8.507 (5) ŵ = 1.04 mm−1
c = 9.216 (5) ÅT = 293 (2) K
α = 108.723 (5)º0.5 × 0.4 × 0.3 mm
β = 108.396 (5)º
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2250 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2064 reflections with I > 2σ(I)
Tmin = 0.601, Tmax = 0.721Rint = 0.015
3041 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034151 parameters
wR(F2) = 0.121H-atom parameters constrained
S = 1.02Δρmax = 0.40 e Å−3
2250 reflectionsΔρmin = −0.57 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50001.00000.50000.02024 (16)
C10.6765 (4)0.6477 (3)−0.1760 (3)0.0260 (5)
C20.6843 (4)0.7807 (3)−0.0285 (3)0.0276 (6)
H2A0.66090.8868−0.03220.033*
C30.7249 (4)0.7538 (3)0.1145 (3)0.0234 (5)
C40.7688 (4)0.5932 (3)0.1253 (3)0.0241 (5)
C50.8169 (4)0.5563 (4)0.2709 (3)0.0316 (6)
H5A0.81860.63860.36660.038*
C60.8610 (5)0.4004 (4)0.2722 (4)0.0363 (7)
H6A0.89360.37790.36890.044*
C70.8573 (4)0.2754 (4)0.1295 (4)0.0342 (6)
H7A0.88820.17020.13200.041*
C80.8084 (4)0.3057 (3)−0.0152 (3)0.0289 (6)
H8A0.80520.2214−0.11020.035*
C90.7636 (4)0.4648 (3)−0.0176 (3)0.0233 (5)
C100.7168 (4)0.8914 (3)0.2641 (3)0.0244 (5)
N10.7143 (3)0.4972 (3)−0.1615 (3)0.0250 (5)
H1A0.70720.4158−0.24830.030*
O10.5726 (3)0.8651 (3)0.3072 (2)0.0319 (5)
O20.8452 (3)1.0169 (3)0.3306 (3)0.0337 (5)
O30.6381 (3)0.6659 (3)−0.3117 (2)0.0342 (5)
O1W0.2409 (3)1.0448 (3)0.3421 (3)0.0331 (5)
H10.12491.02960.34710.050*
H20.25481.13690.32650.050*
O2W0.3413 (3)0.7783 (2)0.4826 (2)0.0274 (4)
H30.26010.82000.53080.041*
H40.40100.72170.54030.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0210 (3)0.0197 (2)0.0201 (2)0.00347 (17)0.01005 (17)0.00379 (17)
C10.0249 (13)0.0306 (14)0.0230 (12)0.0038 (10)0.0085 (10)0.0095 (11)
C20.0327 (14)0.0266 (13)0.0272 (13)0.0085 (11)0.0138 (11)0.0103 (11)
C30.0207 (12)0.0268 (13)0.0229 (12)0.0038 (10)0.0106 (10)0.0056 (10)
C40.0230 (12)0.0274 (13)0.0232 (12)0.0039 (10)0.0097 (10)0.0085 (10)
C50.0353 (15)0.0379 (16)0.0218 (12)0.0064 (12)0.0103 (11)0.0100 (11)
C60.0383 (16)0.0423 (17)0.0331 (15)0.0042 (13)0.0087 (12)0.0226 (13)
C70.0323 (15)0.0287 (14)0.0425 (16)0.0034 (11)0.0071 (12)0.0189 (13)
C80.0274 (13)0.0241 (13)0.0306 (13)0.0029 (10)0.0074 (11)0.0059 (11)
C90.0196 (12)0.0261 (13)0.0237 (11)0.0026 (10)0.0070 (9)0.0081 (10)
C100.0254 (13)0.0264 (13)0.0230 (12)0.0083 (10)0.0117 (10)0.0070 (10)
N10.0294 (12)0.0237 (11)0.0191 (10)0.0037 (9)0.0089 (9)0.0031 (8)
O10.0308 (10)0.0314 (11)0.0293 (10)−0.0013 (8)0.0176 (8)−0.0020 (8)
O20.0316 (11)0.0295 (11)0.0388 (11)−0.0002 (8)0.0197 (9)0.0026 (9)
O30.0412 (12)0.0395 (12)0.0251 (9)0.0082 (9)0.0111 (9)0.0154 (9)
O1W0.0257 (10)0.0366 (11)0.0390 (11)0.0058 (8)0.0100 (8)0.0165 (9)
O2W0.0304 (10)0.0278 (10)0.0263 (9)0.0055 (8)0.0127 (8)0.0094 (8)
Geometric parameters (Å, °) top
Ni1—O1i2.007 (2)C5—H5A0.9300
Ni1—O12.007 (2)C6—C71.393 (5)
Ni1—O1W2.083 (2)C6—H6A0.9300
Ni1—O1Wi2.083 (2)C7—C81.377 (4)
Ni1—O2W2.117 (2)C7—H7A0.9300
Ni1—O2Wi2.117 (2)C8—C91.401 (4)
C1—O31.254 (3)C8—H8A0.9300
C1—N11.351 (4)C9—N11.379 (3)
C1—C21.447 (4)C10—O21.244 (3)
C2—C31.352 (4)C10—O11.250 (3)
C2—H2A0.9300N1—H1A0.8600
C3—C41.433 (4)O1W—H10.8501
C3—C101.514 (3)O1W—H20.8500
C4—C91.405 (4)O2W—H30.8500
C4—C51.414 (4)O2W—H40.8499
C5—C61.371 (4)
O1i—Ni1—O1180.0C6—C5—H5A119.7
O1i—Ni1—O1W90.69 (10)C4—C5—H5A119.7
O1—Ni1—O1W89.31 (10)C5—C6—C7120.4 (3)
O1i—Ni1—O1Wi89.31 (9)C5—C6—H6A119.8
O1—Ni1—O1Wi90.69 (10)C7—C6—H6A119.8
O1W—Ni1—O1Wi180.000 (1)C8—C7—C6120.8 (3)
O1i—Ni1—O2W91.65 (8)C8—C7—H7A119.6
O1—Ni1—O2W88.35 (8)C6—C7—H7A119.6
O1W—Ni1—O2W89.05 (9)C7—C8—C9119.2 (3)
O1Wi—Ni1—O2W90.95 (9)C7—C8—H8A120.4
O1i—Ni1—O2Wi88.35 (8)C9—C8—H8A120.4
O1—Ni1—O2Wi91.65 (8)N1—C9—C8120.0 (2)
O1W—Ni1—O2Wi90.95 (9)N1—C9—C4119.1 (2)
O1Wi—Ni1—O2Wi89.05 (9)C8—C9—C4120.9 (2)
O2W—Ni1—O2Wi180.00 (10)O2—C10—O1126.3 (2)
O3—C1—N1120.0 (2)O2—C10—C3119.9 (2)
O3—C1—C2123.8 (3)O1—C10—C3113.8 (2)
N1—C1—C2116.2 (2)C1—N1—C9124.7 (2)
C3—C2—C1121.4 (3)C1—N1—H1A117.6
C3—C2—H2A119.3C9—N1—H1A117.6
C1—C2—H2A119.3C10—O1—Ni1129.97 (18)
C2—C3—C4120.6 (2)Ni1—O1W—H1123.7
C2—C3—C10120.3 (2)Ni1—O1W—H2113.0
C4—C3—C10119.0 (2)H1—O1W—H2109.1
C9—C4—C5118.1 (3)Ni1—O2W—H3100.1
C9—C4—C3117.9 (2)Ni1—O2W—H4118.4
C5—C4—C3124.0 (2)H3—O2W—H4101.2
C6—C5—C4120.6 (3)
O3—C1—C2—C3179.5 (3)C5—C4—C9—C8−1.2 (4)
N1—C1—C2—C3−0.8 (4)C3—C4—C9—C8178.9 (2)
C1—C2—C3—C42.3 (4)C2—C3—C10—O2−69.5 (4)
C1—C2—C3—C10−175.4 (2)C4—C3—C10—O2112.8 (3)
C2—C3—C4—C9−1.4 (4)C2—C3—C10—O1109.5 (3)
C10—C3—C4—C9176.2 (2)C4—C3—C10—O1−68.2 (3)
C2—C3—C4—C5178.6 (3)O3—C1—N1—C9178.1 (2)
C10—C3—C4—C5−3.7 (4)C2—C1—N1—C9−1.7 (4)
C9—C4—C5—C61.3 (4)C8—C9—N1—C1−177.2 (3)
C3—C4—C5—C6−178.7 (3)C4—C9—N1—C12.5 (4)
C4—C5—C6—C7−0.6 (5)O2—C10—O1—Ni1−4.1 (4)
C5—C6—C7—C8−0.3 (5)C3—C10—O1—Ni1176.92 (17)
C6—C7—C8—C90.5 (4)O1W—Ni1—O1—C10115.2 (3)
C7—C8—C9—N1−180.0 (2)O1Wi—Ni1—O1—C10−64.8 (3)
C7—C8—C9—C40.3 (4)O2W—Ni1—O1—C10−155.7 (3)
C5—C4—C9—N1179.1 (2)O2Wi—Ni1—O1—C1024.3 (3)
C3—C4—C9—N1−0.9 (4)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2Wii0.862.183.031 (3)173
O1W—H1···O2iii0.851.942.783 (3)169
O1W—H2···O3iv0.851.892.722 (3)164
O2W—H3···O2i0.851.902.709 (3)158
O2W—H4···O3v0.851.982.767 (3)154
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) −x+1, −y+2, −z; (i) −x+1, −y+2, −z+1; (v) x, y, z+1.
Table 1
Selected geometric parameters (Å, °) top
Ni1—O12.007 (2)Ni1—O2W2.117 (2)
Ni1—O1W2.083 (2)
O1—Ni1—O1W89.31 (10)O1W—Ni1—O2W89.05 (9)
O1—Ni1—O1Wi90.69 (10)O1Wi—Ni1—O2W90.95 (9)
O1—Ni1—O2W88.35 (8)O1—Ni1—O2Wi91.65 (8)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2Wii0.862.183.031 (3)173
O1W—H1···O2iii0.851.942.783 (3)169
O1W—H2···O3iv0.851.892.722 (3)164
O2W—H3···O2i0.851.902.709 (3)158
O2W—H4···O3v0.851.982.767 (3)154
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) −x+1, −y+2, −z; (i) −x+1, −y+2, −z+1; (v) x, y, z+1.
Acknowledgements top

We thank the Changjiang Scholars and Innovative Research Team in Universities Program, the National Natural Science Foundation of China (grant No. 20573016) and the Science Foundation for Young Teachers of Northeast Normal University (grant No. 20070310) for financial support.

references
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